EP1916270A1 - Heat curable epoxy compositions with blocked polyurethane prepolymers - Google Patents

Abstract

A heat-curable resin composition contains epoxy resin(s) having more than one epoxide group in a molecule, curing agent(s) which is activated at high temperature, and terminally blocked polyurethane prepolymer(s). A heat-curable resin composition contains epoxy resin(s) having more than one epoxide group in a molecule, curing agent(s) which is activated at high temperature, and terminally blocked polyurethane prepolymer(s).

Description

Technical area

The invention relates to the field of impact modifiers and the field of thermosetting epoxy resin compositions.

State of the art

Impact modifiers have long been used to improve the strength of adhesives in the event of sudden impact. In particular, epoxy resin compositions generally have high mechanical strengths, but are very brittle, that is, in a sudden force, such as occurs in a collision of vehicles breaks the cured epoxy resin and leads to destruction of the composite.
Liquid rubbers have long been used for toughening. For example, liquid rubbers based on acrylonitrile / butadiene copolymers, such as those available under the name Hycar®, are used.
EP-B-0 338 985 describes impact-resistant epoxy resin compositions which, in addition to liquid rubbers based on acrylonitrile / butadiene copolymers, additionally comprise liquid rubbers based on polyurethane prepolymers which are terminated with a phenol or a lactam.
WO-A-2005/007766 discloses epoxy resin compositions containing a reaction product of an isocyanate group-terminated prepolymer and a blocking agent selected from the group consisting of bisphenol, phenol, benzyl alcohol, aminophenol or benzylamine. However, such epoxy resin compositions have weaknesses in low temperature impact strength (<0 ° C).
WO-A-03/093387 discloses impact-resistant epoxy resin compositions containing adducts of dicarboxylic acids with glycidyl ethers or bis (aminophenyl) sulfone isomers or aromatic alcohols with glycidyl ethers contain. However, these compositions also have deficiencies in low temperature impact strength (<0 ° C).
WO-A-2004/055092 and WO-A-2005/007720 disclose epoxy resin compositions having improved impact resistance and containing a reaction product of an isocyanate group-terminated polyurethane prepolymer with a monohydroxy epoxide. While these epoxy resin compositions have improved low temperature impact strength over those containing phenolic-terminated polyurethane prepolymers, they are still not optimal.
US 4,701,512 discloses benzoxazolinone and benzoxazine dione as blocking agents for isocyanates and their use as blocked curing agents for epoxy resins, if necessary in combination with catalysts. However, these compositions have no additional curing agents for epoxy resins and are cured at a temperature of 180 ° C to 200 ° C virtually completely over these blocked isocyanates. However, such compositions have insufficient mechanics for adhesives.

Presentation of the invention

It is therefore an object of the present invention to provide heat-curing epoxy resin compositions which have improved impact strength and have high mechanical properties and, in particular, have a high glass transition temperature.
Surprisingly, it has been found that this object can be achieved by a composition according to claim 1. In particular, it was found, surprisingly, that, in particular, the low-temperature impact strength could be greatly increased over the prior art in some cases.
A further aspect of the invention is the use of the terminally blocked polyurethane prepolymer of the formula (1), in particular of the formula (1 '), as an agent for improving the impact resistance, in particular of epoxy resin compositions.
Other aspects are the use of the thermosetting epoxy resin compositions as one-part thermosetting An adhesive, a method of bonding according to claim 30 and the resulting bonded articles.
Particularly preferred embodiments are the subject of the dependent claims.

Ways to carry out the invention

The present invention in a first aspect relates to a thermosetting epoxy resin composition comprising at least one epoxy resin A having on average more than one epoxy group per molecule, at least one curing agent B for epoxy resins which is activated by elevated temperature, and at least one terminally blocked polyurethane prepolymer of the formula (I ) contains.

The thermosetting composition contains at least one epoxy resin A having on average more than one epoxide group per molecule. The epoxide group is preferably present as a glycidyl ether group. The epoxy resin A having an average of more than one epoxy group per molecule is preferably an epoxy liquid resin or a solid epoxy resin. The term "solid epoxy resin" is well known to the person skilled in the art and is used in contrast to "liquid epoxy resins". The glass transition temperature of solid resins is above room temperature, ie they can be comminuted at room temperature to form pourable powders.
Preferred solid epoxy resins have the formula (X)

Here, the substituents R 'and R "are independently of one another either H or CH _3. Furthermore, the subscript s stands for a value of> 1.5, in particular from 2 to 12.
In this document, the use of the term "independently" is in the context of substituents, groups or residues to interpret that in the same molecule the identically named substituents, groups or groups can occur simultaneously with different meaning.

Such solid epoxy resins are commercially available, for example, from Dow or Huntsman or Hexion.
Compounds of formula (X) with an index s between 1 and 1.5 are referred to by the skilled person as semisolid epoxy resins. For the present invention, they are also considered as solid resins. However, preference is given to epoxy resins in the narrower sense, ie where the index s has a value of> 1.5.

Hierbei stehen die Substituenten R'" und R"" unabhängig voneinander entweder für H oder CH₃. Weiterhin steht der Index r für einen Wert von 0 bis 1. Bevorzugt steht r für einen Wert von kleiner als 0.2.
Es handelt sich somit vorzugsweise um Diglycidylether von Bisphenol-A (DGEBA), von Bisphenol-F sowie von Bisphenol-A/F (Die Bezeichnung ,A/F' verweist hierbei auf eine Mischung von Aceton mit Formaldehyd, welche als Edukt bei dessen Herstellung verwendet wird). Solche Flüssigharze sind beispielsweise als Araldite® GY 250, Araldite® PY 304, Araldite® GY 282 (Huntsman) oder D.E.R.™ 331 oder D.E.R.™ 330 (Dow) oder Epikote 828 (Hexion) erhältlich.Preferred liquid epoxy resins have the formula (XI)

Here, the substituents R '"and R""independently of one another are either H or CH _3. Furthermore, the index r stands for a value from 0 to 1. Preferably, r stands for a value of less than 0.2.
It is thus preferably diglycidyl ethers of bisphenol A (DGEBA), bisphenol F and bisphenol A / F (The term 'A / F' refers to a mixture of acetone with formaldehyde, which as starting material in its preparation is used). Such liquid resins are available, for example, as Araldite® GY 250, Araldite® PY 304, Araldite® GY 282 (Huntsman) or DER ™ 331 or DER ™ 330 (Dow) or Epikote 828 (Hexion).

Preferably, the epoxy resin A is an epoxy liquid resin of the formula (XI). In a more preferred embodiment, the thermosetting epoxy resin composition contains both at least one epoxy liquid resin of the formula (XI) and at least one solid epoxy resin of the formula (X).
The proportion of epoxy resin A is preferably 10 to 85% by weight, in particular 15 to 70% by weight, preferably 15 to 60% by weight, of the weight of the composition.

The inventive composition further contains at least one hardener B for epoxy resins, which is activated by elevated temperature. It is preferably a curing agent which is selected from the group consisting of dicyandiamide, guanamines, guanidines, aminoguanidines and derivatives thereof. Also possible are accelerating effective curing agents, such as substituted ureas, such as 3-chloro-4-methylphenylurea (chlorotoluron), or phenyl-dimethylureas, in particular p-chlorophenyl-N, N-dimethylurea (monuron), 3-phenyl-1,1 dimethylurea (fenuron) or 3,4-dichlorophenyl-N, N-dimethylurea (diuron). Furthermore, compounds of the class of imidazoles and amine complexes can be used.
Hardener B is preferably a hardener which is selected from the group consisting of dicyandiamide, guanamine, guanidines, aminoguanidines and derivatives thereof; substituted ureas, in particular 3-chloro-4-methylphenylurea (chlorotoluron), or phenyl-dimethylureas, in particular p-chlorophenyl-N, N-dimethylurea (monuron), 3-phenyl-1,1-dimethylurea (Fenuron), 3,4 Dichlorophenyl N, N-dimethylurea (diuron), as well as imidazoles and amine complexes.
Particularly preferred as curing agent B is dicyandiamide.

Advantageously, the total amount of hardener B is 0.5-12% by weight, preferably 2-8% by weight, based on the weight of the total composition.

Hierbei steht R¹ für ein mit m + m' Isocyanatgruppen terminiertes lineareS oder verzweigtes Polyurethanprepolymer PU1 nach dem Entfernen aller endständigen Isocyanatgruppen. Weiterhin stehen Y¹, Y², Y³ und Y⁴ unabhängig voneinander für H, Halogen, NO₂, Alkyl oder Alkoxy und m steht für einen Wert von 1 bis 8, m' steht für einen Wert von 0 bis 7 und n steht für 0 oder 1. Es gilt die Massgabe, dass m + m' für einen Wert von 2 bis 8 steht.
Weiterhin steht R² unabhängig voneinander für einen Substituenten, welcher ausgewählt ist aus der Gruppe bestehend aus

wobei
R⁵, R⁶, R⁷ und R⁸ je unabhängig voneinander für eine Alkyl- oder Cycloalkyl- oder Aryl- oder Aralkyl- oder Arylalkyl-Gruppe steht oder R⁵ zusammen mit R⁶ oder R⁷ zusammen mit R⁸, einen Teil eines 4- bis 7-gliedrigen Rings bilden, welcher allenfalls substituiert ist;
R⁹, R⁹' und R¹⁰ je unabhängig voneinander für eine Alkyl- oder Aralkyl-oder Aryl- oder Arylalkyl-Gruppe oder für eine Alkyloxy- oder Aryloxy-oder Aralkyloxy-Gruppe steht;
R¹¹ für eine Alkylgruppe steht,
R¹², R¹³ und R¹⁴ je unabhängig voneinander für eine Alkylengruppe mit 2 bis 5 C-Atomen, welche gegebenenfalls Doppelbindungen aufweist oder substituiert ist, oder für eine Phenylengruppe oder für eine hydrierte Phenylengruppe stehen;
R¹⁵, R¹⁶ und R¹⁷ je unabhängig voneinander für H oder für eine Alkylgruppe oder für eine Arylgruppe oder eine Aralkylgruppe stehen; und
R¹⁸ für eine Aralkylgruppe oder für eine ein- oder mehrkernige substituierte oder unsubstituierte Aromatengruppe steht, welche gegebenenfalls aromatische Hydroxylgruppen aufweist; oder für einen Rest der Formel (V') steht

wobei R⁴ unabhängig voneinander für einen Rest eines eine primäre oder sekundäre Hydroxylgruppe enthaltenden aliphatischen, cycloaliphatischen, aromatischen oder araliphatischen Epoxids nach dem Entfernen der Hydroxid- und Epoxidgruppen steht und p für einen Wert von 1, 2 oder 3 steht.The inventive composition further contains a terminally blocked polyurethane prepolymer of the formula (I).

Here, R ¹ stands for a m + m 'isocyanate-terminated linear or branched polyurethane prepolymer PU1 after removal of all terminal isocyanate groups. Furthermore, Y ¹ , Y ² , Y ³ and Y ⁴ are each independently H, halogen, NO ₂ , alkyl or alkoxy and m is a value of 1 to 8, m 'is a value of 0 to 7 and n is for 0 or 1. The rule is that m + m 'stands for a value of 2 to 8.
Furthermore, R ^{2 is} independently a substituent which is selected from the group consisting of

in which
R ⁵ , R ⁶ , R ⁷ and R ^{8 are} each independently an alkyl or cycloalkyl or aryl or aralkyl or arylalkyl group or R ⁵ together with R ⁶ or R ⁷ together with R ⁸ , part of a Form 4- to 7-membered rings, which is at most substituted;
R ⁹ , R ⁹ 'and R ¹⁰ each independently represent an alkyl or aralkyl or aryl or arylalkyl group or an alkyloxy or aryloxy or aralkyloxy group;
R ^{11 is} an alkyl group,
R ¹² , R ¹³ and R ¹⁴ each independently represent an alkylene group having 2 to 5 C atoms, which optionally has double bonds or is substituted, or stand for a phenylene group or for a hydrogenated phenylene group;
R ¹⁵ , R ¹⁶ and R ¹⁷ each independently represent H or an alkyl group, or an aryl group or an aralkyl group; and
R ^{18 is} an aralkyl group or a mono- or polynuclear substituted or unsubstituted aromatic group which optionally has aromatic hydroxyl groups; or represents a radical of the formula (V ')

wherein R ^{4 is} independently a radical of a primary or secondary hydroxyl-containing aliphatic, cycloaliphatic, aromatic or araliphatic epoxide after removal of the hydroxide and epoxide groups and p is 1, 2 or 3.

The dashed lines in the formulas of this document in each case represent the bond between the respective substituent and the associated molecular residue.

auf.
Somit stellt Formel (I) eine umfassende Formel der zwei Formeln (la) und (Ib) dar.

Thus, the terminally blocked polyurethane prepolymer of formula (I) has at least one moiety of the formula

on.
Thus, formula (I) represents a comprehensive formula of the two formulas (Ia) and (Ib).

If Y ¹ , Y ² , Y ³ and / or Y ^{4 is} an alkyl group, this is in particular a linear or branched C ₁ -C ₂₀ -alkyl group.
If Y ¹ Y ² , Y ³ and / or Y ^{4 is} an alkoxy group, this is in particular a linear or branched C ₁ -C ₂₀ -alkoxy group.
Of the substituents Y ¹ , Y ² , Y ³ and Y ^4, preference is given to at least two substituents H. Particular preference is given to Y ¹ = Y ² = Y ³ = Y ⁴ = H.

If R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ^{9 '} , R ¹⁰ , R ¹¹ , R ¹⁵ , R ¹⁶ or R ^{17 is} an alkyl group, this is in particular a linear or branched C ₁ -C ₂₀ alkyl group.
If R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ^{9 '} , R ¹⁰ , R ¹⁵ , R ¹⁶ , R ¹⁷ or R ^{18 is} an aralkyl group, this grouping is in particular a methylene-bonded aromatic group, in particular a benzyl group.

If R ^5, R ^6, R ^7, R ^8, R ^9, R ⁹ 'or R ¹⁰ is an alkylaryl group, this is especially a phenylene residue, bonded via C ₁ - to C ₂₀ alkyl group, such as tolyl or xylyl.

und ---O-R¹⁸. Als Substituent der Formel

ist ε-Caprolactam nach Entfernung des NH-Protons bevorzugt.The radicals R ² are preferably the substituents of the formulas

and --- OR ¹⁸ . As a substituent of the formula

For example, ε-caprolactam is preferred after removal of the NH proton.

Particularly preferred radicals R ² are on the one hand radicals which are selected from the group consisting of

The radical Y in this case represents a saturated or olefinically unsaturated hydrocarbon radical having 1 to 20 C atoms, in particular having 1 to 15 C atoms. As Y, in particular allyl, methyl, nonyl, dodecyl or an unsaturated C15-alkyl radical having 1 to 3 double bonds are preferred.

Hierbei ist als Rest R⁴ insbesondere ein dreiwertiger Rest der Formel

bevorzugt, wobei R für Methyl oder H steht.On the other hand, particularly preferred radicals R ² are radicals of the formula (V ")

In this case, the radical R ^{4 is} in particular a trivalent radical of the formula

preferred, wherein R is methyl or H.

As R ² are on the one hand in particular phenols or bisphenols after removal of a hydroxyl group to consider. Preferred examples of such phenols and bisphenols are, in particular, phenol, cresol, resorcinol, pyrocatechol, cardanol (3-pentadecenylphenol (from cashew nut shell oil)), nonylphenol, phenols reacted with styrene or dicyclopentadiene, bisphenol A, bisphenol -F and 2,2'-diallyl-bisphenol-A.

Particularly preferably, m 'is 0, ie the terminally blocked polyurethane prepolymer of the formula (I) preferably has no substituents R ² . In a particularly preferred embodiment, the terminally blocked polyurethane prepolymer of the formula (I) has the formula (I ').

und allenfalls einer oder mehreren Isocyanat-reaktiven Verbindungen R²H.
Falls mehrere derartige Isocyanat-reaktive Verbindungen eingesetzt werden, kann die Reaktion sequentiell oder mit einer Mischung dieser Verbindungen erfolgen.
Die Umsetzung erfolgt derart, dass die eine oder die mehreren Isocyanat-reaktiven Verbindungen stöchiometrisch oder im stöchiometrischen Überschuss eingesetzt werden, um zu gewährleisten, dass alle NCO-Gruppen umgesetzt sind.The preparation of the terminally blocked polyurethane prepolymer of the formula (I) is carried out from the isocyanate-terminated linear or branched polyurethane prepolymer PU1 with at least one isocyanate-reactive compound of the formula

and at most one or more isocyanate-reactive compounds R ² H.
If several such isocyanate-reactive compounds are used, the reaction can be carried out sequentially or with a mixture of these compounds.
The reaction is carried out in such a way that the one or more isocyanate-reactive compounds are used stoichiometrically or in stoichiometric excess in order to ensure that all NCO groups have reacted.

If R ^{2 has} the formula (V "), the corresponding isocyanate-reactive compounds is a monohydroxyl epoxide compound of the formula (V)

The monohydroxyl epoxy compound of the formula (V) has 1, 2 or 3 epoxide groups. The hydroxyl group of this monohydroxyl epoxy compound (V) may be a primary or a secondary hydroxyl group.
Such monohydroxyl epoxy compounds can be produced, for example, by reacting polyols with epichlorohydrin. Depending on the reaction, the corresponding monohydroxyl epoxide compounds are formed in different concentrations in the reaction of polyfunctional alcohols with epichlorohydrin as by-products. These can be isolated by conventional separation operations. In general, however, it is sufficient to use the product mixture obtained in the glycidylation reaction of polyols from completely and partially reacted to the glycidyl ether polyol. Examples of such hydroxyl-containing epoxides are butanediol monoglycidyl ether (contained in butanediol diglycidyl ether), hexanediol monoglycidyl ether (contained in hexanediol diglycidyl ether), cyclohexanedimethanol glycidyl ether, trimethylolpropane diglycidyl ether (contained as a mixture in trimethylolpropane triglycidyl ether), glycerol diglycidyl ether (contained as a mixture in glycerol triglycidyl ether), pentaerythritol triglycidyl ether (contained as a mixture in pentaerythritol tetraglycidyl ether). Preferably, trimethylolpropane diglycidyl ether, which occurs at a relatively high level in commonly prepared trimethylolpropane triglycidyl ether, is used.
However, it is also possible to use other similar hydroxyl-containing epoxides, in particular glycidol, 3-glycidyloxybenzyl alcohol or hydroxymethyl cyclohexene oxide. Preference is furthermore given to the β-hydroxy ether of the formula (IX) which is present in commercially available liquid epoxy resins prepared from bisphenol A (R =CH ₃ ) and epichlorohydrin and contains about 15%, and the corresponding β-hydroxy ethers of the formula (IX ) formed in the reaction of bisphenol-F (R = H) or the mixture of bisphenol-A and bisphenol-F with epichlorohydrin.

Also preferred are distillation residues, which are obtained in the production of high purity, distilled epoxy liquid resins. Such distillation residues have an up to three times higher concentration of hydroxyl-containing epoxides than commercially available undistilled epoxy liquid resins. In addition, a wide variety of epoxides with a β-hydroxy ether group, prepared by the reaction of (poly) epoxides with a deficit of monovalent nucleophiles such as carboxylic acids, phenols, thiols or sec-amines, can be used.
The free primary or secondary OH functionality of the monohydroxyl epoxide compound of the corresponding formula (V) permits efficient reaction with terminal isocyanate groups of prepolymers without having to use disproportionate excesses of the epoxide component.

The terminally blocked polyurethane prepolymer of the formula (I) advantageously has an elastic character and is furthermore advantageously soluble or dispersible in epoxy liquid resins.

The amount of the terminally blocked polyurethane prepolymer of the formula (I) is advantageously between 1 and 45% by weight, in particular between 3 and 35% by weight, based on the total weight of the thermosetting epoxy resin composition.
The ratio of the number of epoxy groups of the epoxy resin A to the number of blocked isocyanate groups of the terminally blocked polyurethane prepolymer of the formula (1) is more than 5, in particular 5 to 100, preferably 10 to 80. Such compositions react primarily via curing by means of the hardener B. The terminally blocked polyurethane prepolymer of formula (I) contributes only a small amount to the epoxy cure and is used primarily as an impact modifier in the composition.

The polyurethane prepolymer PU1, on which R ¹ is based, can be prepared from at least one diisocyanate or triisocyanate and from a polymer Q _PM with terminal amino, thiol or hydroxyl groups and / or from an optionally substituted polyphenol Q _PP .

Throughout this document, the prefix "poly" in "polyisocyanate", "polyol", "polyphenol" and "polymer kaptan" refers to molecules which formally contain two or more of the respective functional groups.

Suitable diisocyanates are aliphatic, cycloaliphatic, aromatic or araliphatic diisocyanates, in particular commercial products such as methylene diphenyl diisocyanate (MDI), hexamethylene diisocyanate (HDI), toluene diisocyanate (TDI), tolidine diisocyanate (TODI), isophorone diisocyanate (IPDI), trimethylhexamethylene diisocyanate (TMDI), 2,5- or 2,6-bis (isocyanatomethyl) bicyclo [2.2.1] heptane, 1,5-naphthalene diisocyanate (NDI), dicyclohexylmethyl diisocyanate (H ₁₂ MDI), p-phenylene diisocyanate (PPDI), m-tetramethylxylylene diisocyanate (TMXDI), etc. as well as their dimers. Preferred are HDI, IPDI, MDI or TDI.
Suitable triisocyanates are trimers or biurets of aliphatic, cycloaliphatic, aromatic or araliphatic diisocyanates, especially the isocyanurates and biurets of the diisocyanates described in the previous paragraph.
Of course, suitable mixtures of di- or triisocyanates can be used.

As polymers Q _PM with terminal amino, thiol or hydroxyl groups are particularly suitable polymers Q _PM having two or three terminal amino, thiol or hydroxyl groups.

The polymers Q _PM advantageously have an equivalent weight of 300-6000, in particular of 600-4000, preferably of 700-2200 g / equivalent of NCO-reactive groups.

• Polyoxyalkylenpolyole, auch Polyetherpolyole genannt, welche das Polymerisationsprodukt von Ethylenoxid, 1,2-Propylenoxid, 1,2- oder 2,3-Butylenoxid, Tetrahydrofuran oder Mischungen davon sind, gegebenenfalls polymerisiert mit Hilfe eines Startermoleküls mit zwei oder drei aktiven H-Atomen wie beispielsweise Wasser oder Verbindungen mit zwei oder drei OH-Gruppen. Eingesetzt werden können sowohl Polyoxyalkylenpolyole, die einen niedrigen Ungesättigtheitsgrad aufweisen (gemessen nach ASTM D-2849-69 und angegeben in Milliequivalent Ungesättigtheit pro Gramm Polyol (mEq/g)), hergestellt beispielsweise mit Hilfe von sogenannten Double Metal Cyanide Complex Katalysatoren (kurz DMC-Katalysatoren), als auch Polyoxyalkylenpolyole mit einem höheren Ungesättigtheitsgrad, hergestellt beispielsweise mit Hilfe von anionischen Katalysatoren wie NaOH, KOH oder Alkalialkoholaten. Besonders geeignet sind Polyoxypropylendiole und -triole mit einem Ungesättigtheitsgrad tiefer als 0.02 mEq/g und mit einem Molekulargewicht im Bereich von 1000 - 30'000 Dalton, Polyoxybutylendiole und -triole, Polyoxypropylendiole und -triole mit einem Molekulargewicht von 400 - 8'000 Dalton, sowie sogenannte "EO-endcapped" (ethylene oxide-endcapped) Polyoxypropylendiole oder -triole. Letztere sind spezielle Polyoxypropylenpolyoxyethylenpolyole, die beispielsweise dadurch erhalten werden, dass reine Polyoxypropylenpolyole nach Abschluss der Polypropoxylierung mit Ethylenoxid alkoxyliert werden und dadurch primäre Hydroxylgruppen aufweisen.
• Hydroxyterminierte Polybutadienpolyole, wie beispielsweise solche, die durch Polymerisation von 1,3-Butadien und Allylalkohol oder durch Oxidation von Polybutadien hergestellt werden, sowie deren Hydrierungsprodukte;
• Styrol-Acrylnitril gepfropfte Polyetherpolyole, wie sie beispielsweise von Elastogran unter dem Namen Lupranol® geliefert werden;
• Polyhydroxyterminierte Acrylnitril/Butadien-Copolymere, wie sie beispielsweise aus carboxylterminierten Acrylnitril/Butadien-Copolymeren (kommerziell erhältlich unter dem Namen Hycar® CTBN von Nanoresins AG, Deutschland) und Epoxiden oder Aminoalkoholen hergestellt werden können;
• Polyesterpolyole, hergestellt beispielsweise aus zwei- bis dreiwertigen Alkoholen wie beispielsweise 1,2-Ethandiol, Diethylenglykol, 1,2-Propandiol, Dipropylenglykol, 1,4-Butandiol, 1,5-Pentandiol, 1,6-Hexandiol, Neopentylglykol, Glycerin, 1,1,1-Trimethylolpropan oder Mischungen der vorgenannten Alkohole mit organischen Dicarbonsäuren oder deren Anhydriden oder Estern wie beispielsweise Bernsteinsäure, Glutarsäure, Adipinsäure, Korksäure, Sebacinsäure, Dodecandicarbonsäure, Maleinsäure, Fumarsäure, Phthalsäure, Isophthalsäure, Terephthalsäure und Hexahydrophthalsäure oder Mischungen der vorgenannten Säuren, sowie Polyesterpolyole aus Lactonen wie beispielsweise ε-Caprolacton;
• Polycarbonatpolyole, wie sie durch Umsetzung beispielsweise der oben genannten - zum Aufbau der Polyesterpolyole eingesetzten - Alkohole mit Dialkylcarbonaten, Diarylcarbonaten oder Phosgen zugänglich sind.

Suitable polymers Q _PM are polyols, for example the following commercially available polyols or any mixtures thereof:

• Polyoxyalkylenpolyole, also called polyether polyols, which are the polymerization of ethylene oxide, 1,2-propylene oxide, 1,2- or 2,3-butylene oxide, tetrahydrofuran or mixtures thereof, optionally polymerized by means of a starter molecule having two or three active H atoms such For example, water or compounds having two or three OH groups. Both polyoxyalkylene polyols having a low level of unsaturation (measured according to ASTM D-2849-69 and expressed in milliequivalents of unsaturation per gram of polyol (mEq / g)) prepared, for example, with the aid of so-called double metal cyanide complex catalysts (in short DMC) can be used. Catalysts), as well as polyoxyalkylene polyols having a higher degree of unsaturation, prepared for example with the aid of anionic catalysts such as NaOH, KOH or alkali metal alkoxides. Particularly suitable are polyoxypropylene diols and triols having a degree of unsaturation lower than 0.02 meq / g and having a molecular weight in the range of 1000-30,000 daltons, polyoxybutylene diols and triols, polyoxypropylene diols and triols having a molecular weight of 400-8000 daltons. and so-called "EO-endcapped" (ethylene oxide-endcapped) polyoxypropylene diols or triols. The latter are special polyoxypropylene-polyoxyethylene polyols obtained, for example, by alkoxylating pure polyoxypropylene polyols with ethylene oxide after completion of the polypropoxylation and thereby having primary hydroxyl groups.
• Hydroxy-terminated polybutadiene polyols, such as those prepared by polymerization of 1,3-butadiene and allyl alcohol or by oxidation of polybutadiene, and their hydrogenation products;
• Styrene-acrylonitrile grafted polyether polyols, such as those supplied by Elastogran under the name Lupranol®;
• Polyhydroxy-terminated acrylonitrile / butadiene copolymers, as can be prepared for example from carboxyl-terminated acrylonitrile / butadiene copolymers (commercially available under the name Hycar® CTBN from Nanoresins AG, Germany) and epoxides or amino alcohols;
• Polyester polyols prepared, for example, from dihydric to trihydric alcohols, for example 1,2-ethanediol, diethylene glycol, 1,2-propanediol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, glycerol, 1,1,1-trimethylolpropane or mixtures of the abovementioned alcohols with organic dicarboxylic acids or their anhydrides or esters such as succinic, glutaric, adipic, suberic, sebacic, dodecanedicarboxylic, maleic, fumaric, phthalic, isophthalic, terephthalic and hexahydrophthalic or mixtures of the aforementioned acids , and polyester polyols from lactones such as ε-caprolactone;
• Polycarbonate polyols, as they are accessible by reacting, for example, the abovementioned alcohols used to form the polyesterpolyols with dialkyl carbonates, diaryl carbonates or phosgene.

Advantageously, the polymers Q _PM di- or higher functional polyols having OH Equivalentsgewichten of 300 to 6,000 g / OH equivalent, in particular from 600 to 4000 g / OH equivalent, preferably 700 - 2200 g / OH equivalent. Also advantageous are the polyols selected from the group consisting of polyethylene glycols, polypropylene glycols, polyethylene glycol-polypropylene glycol block co-polymers, polybutylene glycols, hydroxyl-terminated polybutadienes, hydroxyl-terminated butadiene / acrylonitrile copolymers, hydroxyl-terminated synthetic rubbers, their hydrogenation products and mixtures of these polyols.
Furthermore, as polymers Q _PM , di- or higher-functional amino-terminated polyethylene ethers, polypropylene ethers, such as those sold under the name Jeffamine® by Huntsman, polybutylene ethers, polybutadienes, butadiene / acrylonitrile copolymers, such as those described under the name Hycar ATBN from Nanoresins AG, Germany, as well as other amino-terminated synthetic rubbers or mixtures of said components.
For certain applications, suitable polymers Q _{PM are} in particular hydroxyl-containing polybutadienes or polyisoprenes or their partially or completely hydrogenated reaction products.

Die Reste Y¹ und Y² stellen einen divalenten organischen Rest dar und die Indizes u und v variieren je nach Stöchiometrieverhältnis von 1 bis typischerweise 5.
Diese Spezies der Formel (VI) oder (VII) können dann wiederum weiterreagiert werden. So kann beispielsweise aus der Spezies der Formel (VI) und einem Diol mit einem divalenten organischen Rest Y³ ein kettenverlängertes Polyurethanprepolymer PU1 der folgenden Formel gebildet werden:

It is also possible that the polymers Q _{PM can} also be chain-extended, as can be carried out in a manner known to the person skilled in the art by the reaction of polyamines, polyols and polyisocyanates, in particular of diamines, diols and diisocyanates.
Using the example of a diisocyanate and a diol, a species of the formula (VI) or (VII) forms, as shown below, depending on the selected stoichiometry.

The radicals Y ¹ and Y ² represent a divalent organic radical and the indices u and v vary from 1 to typically 5, depending on the stoichiometric ratio.
These species of formula (VI) or (VII) can then in turn be further reacted. For example, from the species of formula (VI) and a diol having a divalent organic radical Y ^3, a chain-extended polyurethane prepolymer PU1 of the following formula can be formed:

From the species of formula (VII) and a diisocyanate having a divalent organic radical Y ⁴ , a chain-extended polyurethane prepolymer PU1 of the following formula can be formed:

The indices x and y vary from 1 to typically 5, depending on the stoichiometric ratio, and are in particular 1 or 2.
Furthermore, the species of the formula (VI) can also be reacted with the species of the formula (VII) to form a chain-extended polyurethane prepolymer PU1 having NCO groups.
For the chain extension, in particular diols and / or diamines and diisocyanates are preferred. Of course, it will be understood by those skilled in the art that higher functionality polyols, such as trimethylolpropane or pentaerythritol, or higher functionality polyisocyanates, such as isocyanurates of diisocyanates, can also be used for chain extension.
In the case of the polyurethane prepolymers PU1 in general and in the case of the chain-extended polyurethane prepolymers in particular, it must advantageously be ensured that the prepolymers do not have too high viscosities, in particular if higher functional compounds are used for the chain extension, since this can be converted into the polymers of the formula (I ) or make the application of the composition difficult.

As polymers Q _{PM are} preferred polyols having molecular weights between 600 and 6000 daltons selected from the group consisting of polyethylene glycols, polypropylene glycols, polyethylene glycol-polypropylene glycol block polymers, polybutylene glycols, hydroxyl-terminated polybutadienes, hydroxyl-terminated butadiene-acrylonitrile copolymers and mixtures thereof.

As polymers Q _PM , particular preference is given to α, ω-dihydroxypolyalkylene glycols having C ₂ -C ₆ -alkylene groups or having mixed C ₂ -C ₆ -alkylene groups, which are terminated with amino, thiol or, preferably, hydroxyl groups. Particularly preferred are polypropylene glycols or polybutylene glycols. Also particularly preferred are hydroxyl-terminated polyoxybutylenes.

As polyphenol Q _PP are particularly suitable bis-, tris- and tetraphenols. These are understood to mean not only pure phenols, but optionally also substituted phenols. The type of substitution can be very diverse. In particular, this is understood to mean a substitution directly on the aromatic nucleus to which the phenolic OH group is bonded. Phenols are furthermore not only understood as mononuclear aromatics, but also as polynuclear or condensed aromatics or heteroaromatics which have the phenolic OH group directly on the aromatic or heteroaromatic compounds.
Due to the nature and position of such a substituent, among other things, the reaction necessary for the formation of the polyurethane prepolymer PU1 with isocyanates is influenced.
The bis- and trisphenols are particularly suitable. As bisphenols or trisphenols, for example, 1,4-dihydroxybenzene, 1,3-dihydroxybenzene, 1,2-dihydroxybenzene, 1,3-dihydroxytoluene, 3,5-dihydroxybenzoates, 2,2-bis (4-hydroxyphenyl) propane (= Bisphenol A), bis (4-hydroxyphenyl) methane (= bisphenol-F), bis (4-hydroxyphenyl) sulfone (= bisphenol-S), naphthororcinol, dihydroxynaphthalene, dihydroxyanthraquinone, dihydroxy-biphenyl, 3,3-bis (p -hydroxyphenyl) phthalide, 5,5-bis (4-hydroxyphenyl) hexahydro-4,7-methanoindane, Phenolphthalein, fluorescein, 4,4 '- [bis- (hydroxyphenyl) -1,3-phenylenebis- (1-methyl-ethylidene)] (= bisphenol-M), 4,4' - [bis (hydroxyphenyl) -1 , 4-phenylenebis (1-methyl-ethylidene)] (= bisphenol-P), 2,2'-diallyl-bisphenol-A, diphenols and dicresols prepared by reacting phenols or cresols with diisopropylidenbenzene, phloroglucinol, bile acid esters, Phenol or cresol novolaks with -OH functionality of 2.0 to 3.5 and all isomers of the aforementioned compounds.
Preferred diphenols and dicresols prepared by reacting phenols or cresols with di-isopropylidenbenzene have a chemical structural formula as shown below for cresol, for example:

Particularly preferred are low-volatility bisphenols. Most preferred are bisphenol-M, bisphenol-S and 2,2'-diallyl-bisphenol-A.
Preferably, the Q _{PP has} 2 or 3 phenolic groups.
In a first embodiment, the polyurethane prepolymer PU1 is prepared from at least one diisocyanate or triisocyanate and from a polymer Q _PM with terminal amino, thiol or hydroxyl groups. The preparation of the polyurethane prepolymer PU1 is carried out in a manner known to the polyurethane expert, in particular by using the diisocyanate or triisocyanate in a stoichiometric excess with respect to the amino, thiol or hydroxyl groups of the polymer Q _PM .
In a second embodiment, the polyurethane prepolymer PU1 is prepared from at least one diisocyanate or triisocyanate and from an optionally substituted polyphenol Q _PP . The preparation of the polyurethane prepolymer PU1 takes place in a polyurethane specialist known manner, in particular by the diisocyanate or triisocyanate is used in a stoichiometric excess with respect to the phenolic groups of the polyphenol Q _PP .

In a third embodiment, the polyurethane prepolymer PU1 is prepared from at least one diisocyanate or triisocyanate and from a polymer Q _PM with terminal amino, thiol or hydroxyl groups and from an optionally substituted polyphenol Q _PP . For the production of the polyurethane prepolymer PU1 from at least one diisocyanate or triisocyanate as well as from a polymer Q _PM with terminal amino, thiol or hydroxyl groups and / or from an optionally substituted polyphenol Q _PP different possibilities are available.
In a first process, called "one-pot process", a mixture of at least one polyphenol Q _PP and at least one polymer Q _{PM is} reacted with at least one diisocyanate or triisocyanate in an excess of isocyanate.
In a second process, called "2-step process I", at least one polyphenol Q _{PP is} reacted with at least one diisocyanate or triisocyanate in an isocyanate excess and then with at least one polymer Q _PM in excess.
Finally, in the third process, called "2-step process II", at least one polymer Q _{PM is} reacted with at least one diisocyanate or triisocyanate in an isocyanate excess and subsequently with at least one polyphenol Q _PP in a deficit.
The three methods lead to isocyanate-terminated polyurethane prepolymers PU1, which may differ in the sequence of their building blocks with the same composition. All three methods are suitable, but the "2-Step Method II" is preferred.
If the isocyanate-terminated polyurethane prepolymers PU1 described are built up from difunctional components, it was found that the equivalence ratio of polymer Q _PM / polyphenol Q _{PP is} preferably greater than 1.50 and the equivalence ratio polyisocyanate / (polyphenol Q _PP + polymer Q _PM ) is preferably greater than 1.20.
If the average functionality of the components used is greater than 2, the molecular weight increase is more rapid than in the purely difunctional case. It is clear to the person skilled in the art that the limits of the possible equivalence ratios strongly depend on whether either the selected polymer Q _PM , the polyphenol Q _PP , the polyisocyanate or several of the named components have a functionality> 2. Depending on the different equivalence ratios can be set, the limits of which is determined by the viscosity of the resulting polymers and must be determined experimentally from case to case.
The polyurethane prepolymer PU1 preferably has elastic character and exhibits a glass transition temperature Tg of less than 0 ° C.

The thermosetting epoxy resin composition may further contain a thixotropic agent C based on a urea derivative. In particular, the urea derivative is a reaction product of an aromatic monomeric diisocyanate with an aliphatic amine compound. It is also quite possible to react several different monomeric diisocyanates with one or more aliphatic amine compounds or a monomeric diisocyanate with several aliphatic amine compounds. The reaction product of 4,4'-diphenylmethylene diisocyanate (MDI) with butylamine has proved to be particularly advantageous.
The urea derivative is preferably present in a carrier material. The carrier material may be a plasticizer, in particular a phthalate or an adipate, preferably a diisodecyl phthalate (DIDP) or dioctyl adipate (DOA). The carrier may also be a non-diffusing carrier. This is preferred to ensure as little as possible migration after curing of unregulated components. Preferred non-diffusing carriers are blocked polyurethane prepolymers.
The preparation of such preferred urea derivatives and support materials are described in detail in the patent application EP 1 152 019 A1 described. The support material is advantageously a blocked polyurethane prepolymer PU2, in particular obtained by reacting a trifunctional polyether polyol with IPDI and subsequent blocking of the terminal isocyanate groups with ε-caprolactam.
Advantageously, the total amount of thixotropic agent C is 0-40% by weight, preferably 5-25% by weight, based on the weight of the total composition. The ratio of the weight of the urea derivative to the weight of the possibly present carrier is preferably 2/98 to 50/50, in particular 5 / 95-25 / 75.

The thermosetting epoxy resin composition preferably further contains a liquid rubber D, which is preferably a carboxyl- or epoxy-terminated polymer.
In a first embodiment, this liquid rubber D is a carboxyl- or epoxide-terminated acrylonitrile / butadiene copolymer or a derivative thereof. Such liquid rubbers are commercially available, for example, under the name Hycar® CTBN and CTBNX and ETBN from Nanoresins AG, Germany. The derivatives are in particular epoxy-containing elastomer-modified prepolymers, as under the product line Polydis®, preferably from the product line Polydis® 36 .., by the company Struktol® (Schill + Seilacher Group, Germany) or under the product line Albipox (Nanoresins, Germany) are commercially available suitable.
It is clear to the person skilled in the art that, of course, mixtures of liquid rubbers can also be used, in particular mixtures of carboxyl- or epoxide-terminated acrylonitrile / butadiene copolymers or of derivatives thereof.

In a second embodiment, this liquid rubber D is a polyacrylate liquid rubber which is completely miscible with liquid epoxy resins and does not become microdroplets until the epoxy resin matrix has cured unmixed. Such polyacrylate liquid rubbers are available, for example, under the designation 20208-XPA from Rohm and Haas.

wobei R³ für ein mit m" Isocyanatgruppen terminiertes linearen oder verzweigtes Polyurethanprepolymer PU1' nach dem Entfernen aller endständigen Isocyanatgruppen steht,
R⁴' für einen Rest eines eine primäre oder sekundäre Hydroxylgruppe enthaltenden aliphatischen, cycloaliphatischen, aromatischen oder araliphatischen Epoxids nach dem Entfernen der Hydroxyl- und Epoxidgruppen, steht, p' für die Werte 1, 2 oder 3 und m" für einen Wert von 2 bis 8 steht.
Die Möglichkeiten und Details für die Herstellung des Isocyanatgruppen terminiertes linearen oder verzweigten Polyurethanprepolymers PU1' entsprechen denjenigen, wie sie bereits für das Isocyanatgruppen terminierte lineare oder verzweigte Polyurethanprepolymer PU1 beschrieben wurden.
Die Möglichkeiten für R^4', p' und m" entsprechen denjenigen von R⁴, p und m, wie sie für die Formel (I) resp. Formel (V) vorgängig bereits beschrieben wurden.In a third embodiment, the liquid rubber D is a liquid rubber of the formula (II).

where R ^{3 is} a linear or branched polyurethane prepolymer PU1 ' terminated with m "isocyanate groups after removal of all terminal isocyanate groups,
R ⁴ 'is a radical of a primary or secondary hydroxyl-containing aliphatic, cycloaliphatic, aromatic or araliphatic epoxide after removal of the hydroxyl and epoxide groups, p' is 1, 2 or 3 and m "is 2 to 8 stands.
The possibilities and details for the preparation of the isocyanate-terminated linear or branched polyurethane prepolymer PU1 ' correspond to those which have already been described for the isocyanate-terminated linear or branched polyurethane prepolymer PU1 .
The possibilities for R ^{4 '} , p' and m "correspond to those of R ⁴ , p and m, as already described above for the formula (I) or formula (V).

In a preferred embodiment, the thermosetting epoxy resin composition contains at least one epoxide-functional liquid rubber based on an acrylonitrile / butadiene copolymer and at least one epoxide-functional liquid rubber of the formula (II).

The liquid rubber D is advantageously used in an amount of 1 to 45% by weight, in particular 1 to 25% by weight, based on the weight of the composition.

The heat-curing epoxy resin composition preferably also contains a solid toughener E. A "toughener" is understood here and hereinafter to be an additive to an epoxy resin matrix which is used even at low additions of 0.1-15% by weight, in particular 0.5-8% by weight. %, causes a significant increase in toughness and is thus able to absorb higher bending, tensile, impact or impact stress before the matrix breaks or breaks.
The solid toughener E in a first embodiment is an organic ion-exchanged layered mineral E1.

The ion-exchanged layered mineral E1 may be either a cation-exchanged layered mineral E1c or an anion-exchanged layered mineral E1a .
The cation-exchanged layered mineral E1c is obtained from a layered mineral E1 ', in which at least some of the cations have been replaced by organic cations. Examples of such cation-exchanged layer minerals E1c are in particular those which are described in US Pat US 5,707,439 or in US 6,197,849 are mentioned. Likewise, the process for producing these cation-exchanged layer minerals E1c is described there. Preferred as layer mineral E1 ' is a layered silicate. The layer mineral E1 ' is particularly preferably a phyllosilicate, as described in US Pat US 6,197,849 Column 2, line 38 to column 3, line 5 are described, in particular a bentonite. Layer minerals E1 ' such as kaolinite or a montmorillonite or a hectorite or an illite have proven to be particularly suitable.
At least part of the cations of the layer mineral E1 'is replaced by organic cations. Examples of such cations are n-octylammonium, trimethyldodecylammonium, dimethyldodecylammonium or bis (hydroxyethyl) octadecylammonium or similar derivatives of amines which can be obtained from natural fats and oils; or guanidinium cations or amidinium cations; or cations of the N-substituted derivatives of pyrrolidine, piperidine, piperazine, morpholine, thiomorpholine; or cations of 1,4-diazobicyclo [2.2.2] octane (DABCO) and 1-azobicyclo [2.2.2] octane; or cations of N-substituted derivatives of pyridine, pyrrole, imidazole, oxazole, pyrimidine, quinoline, isoquinoline, pyrazine, indole, benzimidazole, benzoxazole, thiazole phenazine and 2,2'-bipyridine. Also suitable are cyclic amidinium cations, in particular those as described in US Pat US 6,197,849 in column 3, line 6 to column 4, line 67. Cyclic ammonium compounds are characterized by increased thermal stability compared to linear ammonium compounds, as the thermal Hoffmann degradation can not occur in them.
Preferred cation-exchanged layered minerals E1c are known to the person skilled in the art under the term Organoclay or Nanoclay and are commercially available, for example, under the group names Tixogel® or Nanofil® (Southern Chemistry), Cloisite® (Southern Clay Products) or Nanomer® (Nanocor Inc.).

The anion-exchanged layered mineral E1a is in this case obtained from a layered mineral E1 " in which at least some of the anions have been exchanged for organic anions An example of such an anion-exchanged layered mineral E1a is a hydrotalcite E1", in which at least one part the carbonate anions of the intermediate layers have been replaced by organic anions. Another example is functionalized alumoxanes such. In US Pat. No. 6,328,890 described.
It is quite possible that the composition simultaneously contains a cation-exchanged layered mineral E1c and an anion-exchanged layered mineral E1a .

The solid toughener, in a second embodiment, is a block copolymer E2. The block copolymer E2 is obtained from an anionic or controlled radical polymerization of methacrylic acid ester with at least one further olefinic double bond having monomers. Preferred monomers having an olefinic double bond are those in which the double bond is conjugated directly with a heteroatom or with at least one further double bond. In particular, monomers are suitable which are selected from the group comprising styrene, butadiene, acrylonitrile and vinyl acetate. Preference is given to acrylate-styrene-acrylic acid (ASA) copolymers, obtainable, for example, under the name GELOY 1020 from GE Plastics.
Particularly preferred block copolymers E2 are block copolymers of methyl methacrylate, styrene and butadiene. Such block copolymers are available, for example, as triblock copolymers under the group name SBM from Arkema.

The solid toughener E in a third embodiment is a core-shell polymer E3. Core-shell polymers consist of an elastic core polymer and a rigid shell polymer. Particularly suitable core-shell polymers consist of a core (core) of elastic acrylate or butadiene polymer which wraps around a rigid shell of a rigid thermoplastic polymer. This core-shell structure is formed either spontaneously by demixing a block copolymer or is given by the polymerization as latex or suspension polymerization with subsequent grafting. Preferred core-shell polymers are so-called MBS polymers which are commercially available under the trade name Clearstrength ™ from Atofina, Paraloid ™ from Rohm and Haas or F-351 ™ from Zeon.
Particularly preferred are core-shell polymer particles which are already present as a dried polymer latex. Examples of these are GENIOPERL M23A from Wacker with polysiloxane core and acrylate shell, radiation-crosslinked rubber particles of the NEP series, manufactured by Eliokem or Nanoprene from Lanxess or Paraloid EXL from Rohm and Haas.
Further comparable examples of core-shell polymers are offered under the name Albidur ™ by Nanoresins AG, Germany.

The solid toughener E in a fourth embodiment is a solid reaction product E4 of a carboxylated solid nitrile rubber with excess epoxy resin.

As solid toughener E core-shell polymers are preferred.

The thermosetting epoxy resin composition may contain the solid core-shell polymer E3 , in particular in an amount of 0.1-15% by weight, preferably 1-8% by weight, based on the weight of the composition.

In a further preferred embodiment, the composition additionally contains at least one filler F. This is preferably mica, talc, kaolin, wollastonite, feldspar, syenite, chlorite, bentonite, montmorillonite, calcium carbonate (precipitated or ground), dolomite, quartz, silicic acids (pyrogenic or precipitated), cristobalite, calcium oxide, aluminum hydroxide, magnesium oxide, ceramic hollow spheres, glass hollow spheres, organic hollow spheres, glass spheres, color pigments. Filler F is meant to mean both the organic coated and the uncoated commercially available and known to those skilled forms.
Advantageously, the total content of the total filler F is 3-50% by weight, preferably 5-35% by weight, especially 5-25% by weight, based on the weight of the total composition.

In another preferred embodiment, the composition contains a physical or chemical blowing agent, such as that available under the tradename Expancel ™ from Akzo Nobel or Celogen ™ from Chemtura. The proportion of blowing agent is advantageously 0.1 to 3 wt .-%, based on the weight of the composition.

• Glycidylether von monofunktionellen gesättigten oder ungesättigten, verzweigten oder unverzweigten, zyklischen oder offenkettigen C₄ - C₃₀ Alkoholen, z.B. Butanolglycidylether, Hexanolglycidylether, 2-Ethylhexanolglycidylether, Allylglycidylether, Tetrahydrofurfuryl- und Furfurylglycidylether, Trimethoxysilylglycidylether etc.
• Glycidylether von difunktionellen gesättigten oder ungesättigten, verzweigten oder unverzweigten, zyklischen oder offenkettigen C₂ - C₃₀ Alkolen, z.B Ethylenglykol-, Butandiol-, Hexandiol-, Oktandiolgylcidylether, Cyclohexandimethanoldigylcidylether, Neopentylglycoldiglycidylether etc.
• Glycidylether von tri- oder polyfunktionellen, gesättigten oder ungesättigten, verzweigten oder unverzweigten, zyklischen oder offenkettigen Akoholen wie epoxidiertes Rhizinusöl, epoxidiertes Trimethylolpropan, epoxidiertes Pentaerythrol oder Polyglycidylether von aliphatischen Polyolen wie Sorbitol, Glycerin, Trimethylolpropan etc.
• Glycidylether von Phenol- und Anilinverbindungen wie Phenylglycidylether, Kresylglycidylether, p-tert.-Butylphenylglycidylether, Nonylphenolglycidylether, 3-n-Pentadecenyl-glycidylether (aus Cashewnuss-Schalen-Öl), N,N-Diglycidylanilin etc.
• Epoxidierte Amine wie N, N-Diglycidylcyclohexylamin etc.
• Epoxidierte Mono- oder Dicarbonsäuren wie Neodecansäure-glycidylester, Methacrylsäureglycidylester, Benzoesäureglycidylester, Phthalsäure-, Tetra- und Hexahydrophthalsäurediglycidylester, Diglycidylester von dimeren Fettsäuren etc.
• Epoxidierte di- oder trifunktionelle, nieder- bis hochmolekulare Polyetherpolyole wie Polyethylenglycol-diglycidylether, Polypropyleneglycol-diglycidylether etc.

In a further preferred embodiment, the composition additionally contains at least one epoxide group-carrying Reactive diluents G. These reactive diluents G are in particular:

• Glycidyl ethers of monofunctional saturated or unsaturated, branched or unbranched, cyclic or open-chain C ₄ -C ₃₀ alcohols, for example butanol glycidyl ether, hexanol glycidyl ether, 2-ethylhexanol glycidyl ether, allyl glycidyl ether, tetrahydrofurfuryl and furfuryl glycidyl ether, trimethoxysilyl glycidyl ether etc.
• Glycidyl ethers of difunctional saturated or unsaturated, branched or unbranched, cyclic or open-chain C ₂ -C ₃₀ -alcohols, for example ethylene glycol, butanediol, hexanediol, octanediol glycidyl ethers, cyclohexanedimethanol diglycidyl ethers, neopentylglycol diglycidyl ethers, etc.
• Glycidyl ethers of trifunctional or polyfunctional, saturated or unsaturated, branched or unbranched, cyclic or open-chain alcohols such as epoxidized castor oil, epoxidized trimethylolpropane, epoxidized pentaerythrol or polyglycidyl ethers of aliphatic polyols such as sorbitol, glycerol, trimethylolpropane etc.
• Glycidyl ethers of phenolic and aniline compounds such as phenyl glycidyl ether, cresyl glycidyl ether, p-tert-butylphenyl glycidyl ether, nonyl phenol glycidyl ether, 3-n-pentadecenyl glycidyl ether (from cashew nut shell oil), N, N-diglycidyl aniline, etc.
• Epoxidized amines such as N, N-diglycidylcyclohexylamine etc.
• Epoxidized mono- or dicarboxylic acids such as glycidyl neodecanoate, glycidyl methacrylate, glycidyl benzoate, diglycidyl phthalate, tetra- and hexahydrophthalate, diglycidyl esters of dimer fatty acids, etc.
• Epoxidized di- or trifunctional, low to high molecular weight polyether polyols such as polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether etc.

Particularly preferred are hexanediol diglycidyl ethers, cresyl glycidyl ethers, p-tert-butylphenyl glycidyl ethers, polypropylene glycol diglycidyl ethers and polyethylene glycol diglycidyl ethers.

Advantageously, the total proportion of epoxide group-carrying reactive diluent G is 0.5-20% by weight, preferably 1-8% by weight, based on the weight of the total composition.

The composition may comprise other ingredients, especially catalysts, heat and / or light stabilizers, thixotropic agents, plasticizers, solvents, mineral or organic fillers, blowing agents, dyes and pigments.

It has been found that the novel thermosetting epoxy resin compositions are particularly suitable as one-component adhesives. Thus, in a further aspect, the invention relates to a use of the above-described thermosetting epoxy resin composition as a one-component thermosetting adhesive. Such a one-component adhesive has a wide range of uses. In particular, this thermosetting one-component adhesives are feasible, which are characterized by high impact strength, both at higher temperatures and especially at low temperatures, in particular between 0 ° C to -40 ° C. Such adhesives are needed for bonding heat stable materials. Heat-stable materials are materials which are dimensionally stable at a curing temperature of 100-220 ° C., preferably 120-175 ° C., at least during the curing time. In particular, these are metals and plastics such as ABS, polyamide, polyphenylene ethers, composite materials such as SMC, unsaturated polyester GRP, epoxy or acrylate composites. Preferred is the application in which at least one material is a metal. Particularly preferred use is the bonding of the same or different metals, especially in the shell in the automotive industry. The preferred metals are, above all, steel, in particular electrolytically galvanized, hot-dip galvanized, oiled steel, Bonazink-coated steel, and subsequently phosphated steel, as well as aluminum, in particular in the variants typically occurring in the automobile industry.

With an adhesive based on a heat-curing composition according to the invention, it is possible to achieve the desired combination of high crash resistance both high and low operating temperature. In addition, the composition has high mechanical values. In particular, it has been found that glass transition temperatures of over 95 ° C, in particular of 100 ° C or higher, can be achieved, which is particularly important for applications with high operating temperatures.
A further aspect of the invention thus relates to a method for bonding heat-stable materials, in which these materials are contacted with a previously described epoxy resin composition and which comprises one or more curing steps at a temperature of 100-220 ° C., preferably 120-175 ° C. includes. Such an adhesive is in particular first contacted with the materials to be bonded at a temperature of between 10 ° C and 80 ° C, in particular between 10 ° C and 60 ° C, and later cured at a temperature of typically 100-220 ° C, preferably 120 - 175 ° C. It is particularly important that the curing can take place even at relatively low temperatures, ie at temperatures between 120 and 160 ° C. This is particularly advantageous under energy technology and material technology aspects.

From such a method for bonding heat-stable materials results in a bonded article, which is another aspect of the present invention. Such an article is preferably a vehicle or an attachment of a vehicle.
Of course, in addition to heat-curing adhesives, sealants or coatings can also be realized with a composition according to the invention. Furthermore, the novel compositions are not only suitable for the automotive industry but also for other applications. Particularly noteworthy are related applications in transport engineering such as ships, trucks, buses or rail vehicles or in the construction of consumer goods such as washing machines.

The materials bonded by means of a composition according to the invention are used at temperatures between typically 120 ° C. and -40 ° C., preferably between 100 ° C. and -40 ° C., in particular between 80 ° C. and -40 ° C.

It has been found that the terminally blocked polyurethane prepolymer of the formula (I) can be used in an outstanding manner as an impact modifier, that is to say as an agent for improving the impact resistance, in particular in epoxy resins.

Compositions can be formulated which typically have fracture energies, measured to ISO 11343, of greater than 15.0 J at 23 ° C and greater than 7.0 J at -30 ° C. It is sometimes possible to formulate compositions having fracture energies greater than 17.5 J at 23 ° C and greater than 12.0 J at -30 ° C. Particularly advantageous compositions have even fracture energies of more than 18.0 J at 23 ° C and more than 12.0 J at -30 ° C.

A particularly preferred application of the inventive thermosetting epoxy resin composition is the application as a thermosetting structural adhesive in vehicle construction.

Examples

In the following, some examples will be shown, which further illustrate the invention, but are not intended to limit the scope of the invention in any way. The raw materials used in the examples are listed in Table 1. Table 1. Raw materials used. Used raw materials supplier DER 330 (bisphenol A diglycidyl ether = "DGEBA") Dow DER 671 ("Type 1" solid resin) (EP equivalent weight 475-550g / eq) Dow Albipox XP 23/0277 ("Albipox") Nanoresins Polypox R7 (tert-butylphenyl glycidyl ether) UPPC dicyandiamide Degussa Poly-THF 2000 (difunctional polybutylene glycol) BASF (OH equivalent weight = approx. 1000 g / OH equivalent) Poly-THF 1800 (Difunctional polybutylene glycol) BASF (OH equivalent weight = approx. 900 g / OH equivalent) Liquiflex H (hydroxyl terminated polybutadiene) Krahn (OH equivalent weight = approx. 1230 g / OH equivalent) Caradol ED56-10 (Difunctional Polypropylene Glycol) Shell (OH equivalent weight = approx. 1000 g / OH equivalent) Isophorone diisocyanate (= IPDI) Degussa-Huls 2-Benzoxazolinone Sigma-Aldrich ε-caprolactam EMS chemistry Cardolite NC-700 (Cardanol, meta-substituted alkenyl-mono-phenol) Cardolite® 2,2'-diallyl Bisphenol A Sigma-Aldrich F-351 ™ (Core-Shell Polymer) Zeon

Exemplary preparation of a monohydroxyl-containing epoxide MHE

Trimethylolpropane glycidyl ether was prepared according to the method in patent US 5,668,227 , Example 1, prepared from trimethylolpropane and epichlorohydrin with tetramethylammonium chloride and sodium hydroxide. A yellowish product having an epoxide number of 7.5 eq / kg and a hydroxyl group content of 1.8 eq / kg is obtained. It can be concluded from the HPLC-MS spectrum that essentially a mixture of trimethylolpropane diglycidyl ether and trimethylolpropane triglycidyl ether is present. This product was used as MHE .

Examples of the preparation of terminally blocked polyurethane prepolymers of the formula (I) Polyurethane prepolymer PU1-1

150 g of poly-THF 2000 (OH number 57 mg / g KOH) and 150 Liquiflex H (OH number 46 mg / g KOH) were dried under vacuum at 105 ° C for 30 minutes. After the temperature was reduced to 90 ° C, 64.0 g of IPDI and 0.13 g of dibutyltin dilaurate were added. The reaction was carried out under reduced pressure at 90 ° C. until the NCO content remained constant at 3.30% after 2.5 h (calculated NCO content: 3.38%).

Polyurethane prepolymer PU1-2

300 g poly-THF 2000 (OH number 57 mg / g KOH) were dried under vacuum at 105 ° C for 30 minutes. After the temperature was reduced to 90 ° C, 70.7 g of IPDI and 0.13 g of dibutyltin dilaurate were added. The reaction was carried out under vacuum at 90 ° C. until the NCO content remained constant at 3.50% after 2.5 h (calculated NCO content: 3.67%).

Polyurethane prepolymer PU1-3 (pre-extended)

To 370.7 g of polyurethane prepolymer PU1-2 was added 22.9 g of 2,2'-diallylbisphenol-A as a pre-extender. The mixture was stirred at 90 ° C. for 3 h under vacuum until the NCO content remained constant at 1.70% (calculated NCO content: 1.87%).

BlockPrep-1

To 364.0 g of polyurethane prepolymer PU1-1 was added 46.4 g of 2-benzoxazolinone as a blocking agent. It was further stirred at 105 ° C under vacuum until the NCO content had dropped below 0.1% after 3.5 h.

BlockPrep-2

To 370.7 g of polyurethane prepolymer PU1-2 was added 50.1 g of 2-benzoxazolinone as a blocking agent. It was further stirred at 105 ° C under vacuum until the NCO content had dropped below 0.1% after 3.5 h.

BlockPrep-3

To 393.6 g of polyurethane prepolymer PU1-3 was added 25.8 g of 2-benzoxazolinone as a blocking agent. It was further stirred at 105 ° C under vacuum until the NCO content had dropped below 0.1% after 3.5 h.

BlockPrep-R1

To 364.0 g of the polyurethane prepolymer PU1-1 38.8 g of ε-caprolactam were added as a blocking agent. It was further stirred at 105 ° C under vacuum until the NCO content had dropped below 0.1% after 3.5 h.

BlockPre-R2

To 364.0 g of polyurethane prepolymer PU1-1 was added 103.0 g of Cardolite NC-700 as a blocking agent. It was further stirred at 105 ° C under vacuum until the NCO content had dropped below 0.1% after 3.5 h.

BlockPrep-R3

To 370.7 g of polyurethane prepolymer PU1-2 was added 114.3 g of 2,2'-diallylbisphenol-A as a blocking agent. It was further stirred at 105 ° C under vacuum until the NCO content had dropped below 0.1% after 3.5 h.

BlockPrep-R4

To 370.7 g of the polyurethane prepolymer PU1-2 were added 41.9 g of ε-caprolactam as a blocking agent. It was further stirred at 105 ° C under vacuum until the NCO content had dropped below 0.1% after 3.5 h.

BlockPrep-R5

To 370.7 g of polyurethane prepolymer PU1-2 was added 111.2 g of Cardolite NC-700 as a blocking agent. It was further stirred at 105 ° C under vacuum until the NCO content had dropped below 0.1% after 3.5 h.

Example of the preparation of a liquid rubber based on an epoxy group-terminated polyurethane prepolymer of the formula (II) ( EP1 )

160 g of PolyTHF 1800 (OH number 62.3 m / g KOH), 110 g of Liquiflex H (OH number 46 mg / g KOH) and 130 g of Caradol ED 56-10 (OH number 56 mg / g KOH) were added 30 minutes dried under vacuum at 105 ° C. After the temperature was reduced to 90 ° C, 92.5 g of IPDI and 0.08 g of dibutyltin dilaurate were added. The reaction was carried out under reduced pressure at 90 ° C. until the NCO content remained constant at 3.60% after 2.5 h (calculated NCO content: 3.62%). Subsequently, to this polyurethane prepolymer 257.8 g of MHE described above were added and the reaction was continued at 90 ° C under vacuum until no more NCO content was measured.

Preparation of the compositions

According to Table 2, the reference compositions Ref. 1 - Ref. 11 and the novel compositions 1, 2, 3, 4, 5, 6 and 7 were prepared.
The amount of dicyandiamide was adjusted in each case to the epoxide group concentration.

Test Methods: Tensile shear strength (ZSF) (DIN EN 1465)

The test specimens were made of the described compositions and electrolytically galvanized DC04 steel (eloZn) with the dimensions 100 x 25 x 1.5 mm produced, while the adhesive surface was 25 x 10 mm at a layer thickness of 0.3 mm. Hardened for 30 min. At 175 ° C. The pulling speed was 10 mm / min.

Tensile strength (ZF) (DIN EN ISO 527)

An adhesive sample was pressed between two Teflon papers to a layer thickness of 2 mm. Subsequently, the adhesive was cured for 30 minutes at 175 ° C. The Teflon papers were removed and the test specimens to DIN standard were punched out in the hot state. The specimens were measured after 1 day storage under standard conditions at a pulling speed of 2 mm / min.
The tensile strength was determined according to DIN EN ISO 527.

Percussion peeling (ISO 11343)

The test specimens were produced from the compositions described and with electrolytically galvanized DCO 4 steel (eloZn) with the dimensions 90 × 20 × 0.8 mm, the bond area being 20 × 30 mm and a layer thickness of 0.3 mm. Hardened for 30 min. At 175 ° C. The measurement of the Schlagschälarbeit was carried out in each case at room temperature and at -30 ° C. The impact velocity was 2 m / s. The fracture energy (BE) in joules is the area under the measurement curve (from 25% to 90%, according to ISO 11343).

Glass transition temperature (T. _G )

The glass transition temperature was determined by DSC. A device Mettler DSC822 ^{e was} used for this purpose. 20-30 mg adhesive samples were each weighed into an aluminum crucible. After the sample had been cured in the DSC for 30 min. At 175 ° C, the sample was cooled to -20 ° C and then heated at a heating rate of 20 ° C / min to 150 ° C. The glass transition temperature was determined by DSC software from the measured DSC curve.

The results of these tests are summarized in Table 2.

Claims (33)

A thermosetting epoxy resin composition containing at least one epoxy resin A having on average more than one epoxide group per molecule; - At least one hardener B for epoxy resins, which is activated by elevated temperature. at least one terminally blocked polyurethane prepolymer of the formula (I)

wherein R ^{1 stands} for a m + m 'isocyanate-terminated linear or branched polyurethane prepolymer PU1 after removal of all terminal isocyanate groups;
Y ¹ , Y ² , Y ³ and Y ^{4 are} independently H, halogen, NO ₂ alkyl or alkoxy;
and wherein R ^{2 is} independently a substituent selected from the group consisting of

in which
R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent an alkyl or cycloalkyl or aryl or aralkyl or arylalkyl group
or R ⁵ together with R ⁶ or R ⁷ together with R ⁸ form part of a 4- to 7-membered ring which is at most substituted;
R ⁹ , R ⁹ 'and R ¹⁰ each independently represent an alkyl or aralkyl or aryl or arylalkyl group or an alkyloxy or aryloxy or aralkyloxy group;
R ^{11 is} an alkyl group,
R ¹² , R ¹³ and R ¹⁴ each independently represent an alkylene group having 2 to 5 C atoms, which optionally has double bonds or is substituted, or stand for a phenylene group or for a hydrogenated phenylene group;
R ¹⁵ , R ¹⁶ and R ¹⁷ each independently represent H or an alkyl group, or an aryl group or an aralkyl group; and
R ^{18 is} an aralkyl group or a mono- or polynuclear substituted or unsubstituted aromatic group which optionally has aromatic hydroxyl groups; or for a remainder of the formula

stands,
wherein R ^{4 is} independently a radical of a primary or secondary hydroxyl group-containing aliphatic, cycloaliphatic, aromatic or araliphatic epoxide after removal of the hydroxide and epoxide groups and p is 1, 2 or 3;
and wherein n is 0 or 1;
m is a value of 1 to 8 and m 'is a value of 0 to 7, with the proviso that m + m' is a value of 2 to 8. A thermosetting epoxy resin composition according to claim 1, characterized in that Y ¹ = Y ² = Y ³ = Y ⁴ = H. A thermosetting epoxy resin composition according to claim 1 or 2, characterized in that n = 0. A thermosetting epoxy resin composition according to any one of the preceding claims, characterized in that m '= 0. A thermosetting epoxy resin composition according to any one of the preceding claims, characterized in that R ^{2 is} a substituent of the formula

--- OR ¹⁸ stands.

A thermosetting epoxy resin composition according to claim 5, characterized in that R ^{2 is} selected from the group consisting of

where Y is a saturated or olefinically unsaturated hydrocarbon radical having 1 to 20 C atoms, in particular having 1 to 15 C atoms. A thermosetting epoxy resin composition according to claim 5, characterized in that R ^{2 is} a substituent of the formula

wherein R ^{4 is} preferably a trivalent radical of the formula

is where R is methyl or H. A thermosetting epoxy resin composition according to any one of the preceding claims, characterized in that the polyurethane prepolymer PU1 is prepared from at least one diisocyanate or triisocyanate and
from a polymer Q _PM with terminal amino, thiol or hydroxyl groups;
and or
from an optionally substituted polyphenol Q _PP . A thermosetting epoxy resin composition according to claim 8, characterized in that the polymer Q _{PM has} 2 or 3 terminal amino, thiol or hydroxyl groups. A thermosetting epoxy resin composition according to claim 8 or 9, characterized in that the polymer Q _{PM is} an α, ω-Dihydroxypolyalkylenglykol with C ₂ -C ₆ alkylene or with mixed C ₂ -C ₆ - alkylene groups, which with amino, thiol or , preferably, hydroxyl groups is terminated. A thermosetting epoxy resin composition according to claim 8 or 9, characterized in that the polymer Q _{PM is} a hydroxyl group-containing polybutadiene or polyisoprene or a partially or fully hydrogenated reaction product thereof. A thermosetting epoxy resin composition according to any one of claims 8 to 11, characterized in that the polymer Q _{PM has} an OH equivalent weight of 300-6,000 g / OH equivalent, in particular 700-2200 g / OH equivalent. A thermosetting epoxy resin composition according to any one of claims 8 to 12, characterized in that the polyphenol Q _{PP has} 2 or 3 phenolic groups. Heat-curing epoxy resin composition according to any one of claims 8 to 13, characterized in that the diisocyanate or triisocyanate used for the preparation of the polyurethane prepolymer PU1 is a diisocyanate, preferably HDI, IPDI, MDI or TDI. A thermosetting epoxy resin composition according to any one of the preceding claims, characterized in that the terminally blocked polyurethane prepolymer of the formula (I) has the formula (1 ').

A thermosetting epoxy resin composition according to any one of the preceding claims, characterized in that the curing agent B is a curing agent selected from the group consisting of dicyandiamide, guanamines, guanidines, aminoguanidines and their derivatives; substituted ureas, in particular 3-chloro-4-methylphenylurea (chlorotoluron), or phenyl-dimethylureas, in particular p-chlorophenyl-N, N-dimethylurea (monuron), 3-phenyl-1,1-dimethylurea (Fenuron), 3,4 Dichlorophenyl N, N-dimethylurea (diuron), as well as imidazoles and amine complexes. A thermosetting epoxy resin composition according to any one of the preceding claims, characterized in that the composition further contains at least one thixotropic agent C, based on urea derivative in a carrier material, in particular in an amount of 0-40 wt .-%, based on the weight of the composition. A thermosetting epoxy resin composition according to any one of the preceding claims, characterized in that the composition further comprises at least one liquid rubber D, which is a carboxyl or epoxy-terminated polymer, in particular a carboxyl- or epoxy-terminated acrylonitrile / butadiene copolymer, in particular in an amount from 1 to 45% by weight, based on the weight of the composition. A thermosetting epoxy resin composition according to claim 18, characterized in that the liquid rubber D has the formula (II)

where R ^{3 is} a m or isocyanate-terminated linear or branched polyurethane prepolymer PU1 'after removal of all terminal isocyanate groups,
R ^4, for a radical of a primary or secondary hydroxyl group-containing aliphatic, cycloaliphatic, aromatic or araliphatic epoxide after removal of the hydroxyl and epoxide groups, stands p 'for the values 1, 2 or 3 and m "for a value of 2
to 8 stands. A thermosetting epoxy resin composition according to claim 19, characterized in that the thermosetting epoxy resin composition contains at least one epoxide functional liquid rubber based on an acrylonitrile / butadiene copolymer and at least one epoxide functional liquid rubber of the formula (II). A thermosetting epoxy resin composition according to any one of the preceding claims, characterized in that the composition further comprises a solid toughener E, in particular in an amount of 0.1-15 wt .-%, in particular from 0.5 to 8 wt .-%, based on the weight of the composition, contains. A thermosetting epoxy resin composition according to claim 21, characterized in that the solid toughness modifier E is a core-shell polymer. A thermosetting epoxy resin composition according to any one of the preceding claims, characterized in that the composition further contains at least one filler F, in particular in an amount of 3 - 50 wt .-%, based on the weight of the composition. A thermosetting epoxy resin composition according to any one of the preceding claims, characterized in that the composition at least one propellant, in particular in an amount of 0.1 to 3 wt .-%, based on the weight of the composition contains. A thermosetting epoxy resin composition according to any one of the preceding claims, characterized in that the composition further contains an epoxy group-carrying reactive diluent G, in particular in an amount of 0.5-20 wt .-%, based on the weight of the composition. A thermosetting epoxy resin composition according to any one of the preceding claims, characterized in that the proportion of the epoxy resin A is 10 - 85 wt .-%, in particular 15-70 wt .-%, preferably 15-60 wt .-%, by weight of the composition. A thermosetting epoxy resin composition according to any one of the preceding claims, characterized in that the proportion of the terminally blocked polyurethane prepolymer of the formula (1) is 1 - 45 wt .-%, in particular 3-35 wt .-%, by weight of the composition. Use of the terminal-blocked polyurethane prepolymer of the formula (I), in particular of the formula (I ') as described in the thermosetting epoxy resin composition according to any one of Claims 1 to 27, as an impact-improving agent, in particular of epoxy resin compositions. Use of a thermosetting epoxy resin composition according to any one of claims 1 to 27 as a one-component thermosetting adhesive, in particular as a thermosetting structural adhesive in vehicle construction. A method for bonding heat-stable materials, in particular of metals, characterized in that these materials with a thermosetting epoxy resin composition according to any one of claims 1 to 27 and comprises one or more curing steps at a temperature of 100-220 ° C, preferably 120-175 ° C. A method of bonding according to claim 30, characterized in that the materials are contacted with a thermosetting epoxy resin composition according to any one of claims 1 to 23 and that after bonding the bonded materials at temperatures between 120 ° C and -40 ° C, preferably between 100 ° C and -40 ° C, in particular between 80 ° C and -40 ° C are used. Adhesive article obtained by a process according to claim 30 or 31. Glued article according to claim 32, characterized in that the article is a vehicle or an attachment of a vehicle.